Naphthol derivatives and process for producing the same

ABSTRACT

A naphthol derivative represented by the general formula (I)  wherein Y and Y&#39; indicate --(CONH) n  --X or --COR; X is a phenyl group, a naphthyl group, an anthraquinonyl group, a benzimidazolonyl group or a carbazolyl group; R is a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a benzyloxy group, a phenyloxy group or a phenacyloxy group; R 2  is a hydrogen atom, an alkaline metal, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenylalkyl group; Z is a group selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a nitroso group and an amino group (Z may be substituted on any ring of the naphthalene ring); and n is an integer of 1 or 2; provided that R 2  and Z do not simultaneously indicate a hydrogen atom when both R simultaneously indicate a hydroxyl group!, and a process for producing the same. This naphthol derivative can be used as raw materials for synthesis, such as dyes, pigments, photosensitive materials and the like. ##STR1##

This is a divisional of application Ser. No. 08/764,269, now pendingfiled Dec. 12, 1996.

TECHNICAL FIELD

The present invention relates to a novel naphthol derivatives which canbe used as raw materials etc. for synthesis, such as dyes, pigments,photosensitive materials and the like, and a process for producing thesame.

BACKGROUND ART

The naphthol derivatives is the cheapest among condensed aromaticcompounds which form a conjugated polyene system and has absorption inthe electron band, and is easily used as raw materials for synthesis.Therefore, it has hitherto been used as various peculiar compounds,particularly raw materials such as dyes, pigments, photosensitivematerials and the like.

As the naphthol derivatives like this, for example, there have beenknown 2-hydroxy-3-phenylaminocarbonylnaphthalene or2-hydroxy-6-phenylaminocarbonylnaphthalene wherein a substituent isintroduced at the 3-position or 6-position of 2-hydroxynaphthalene, andthose wherein an alkyl or alkoxy group is added to these phenyl groups.

But as the naphthalene derivative which has substituents at both the3-position and 6-position of 2-hydroxynaphthalene,2-hydroxy-3,6-dihydroxycarbonylnaphthalene is merely known.

An object of the present invention is to provide novel derivatives of3,6-di-substituted-2-hydroxynaphthalene, particularly2-hydroxy-3,6-dihydroxycarbonylnaphthalene, which is useful as rawmaterials for synthesis, and a process for synthesizing the same.

DISCLOSURE OF THE INVENTION

The present invention relates to naphthol derivatives represented by thegeneral formula (I): ##STR2## wherein Y is --(CONH)_(n) --X or --COR; Y'is --(CONH)_(n) --X' or --COR';

X and X' may be the same or different and indicate a phenyl group, anaphthyl group, an anthraquinonyl group, a benzimidazolonyl group or acarbazolyl group, and each group may be optionally substituted;

R and R' may be the same or different and indicate a hydroxyl group, anoptically branched alkoxy group having 1 to 6 carbon atoms, a halogenatom, a benzyloxy group, a phenyloxy group or a phenacyloxy group;

R₂ is a hydrogen atom, an alkaline metal, an optionally branched alkylgroup having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbonatoms or a phenylalkylene group;

Z indicate one or more sorts of groups selected from the groupconsisting of a hydrogen atom, a halogen atom, a nitro group, a nitrosogroup and an amino group (Z may be substituted on any ring of thenaphthalene ring); and

n is an integer of 1 or 2;

provided that R₂ and Z are not simultaneously hydrogen atom when R andR' simultaneously are hydroxyl group!, and a process for producing thesame.

Particularly, the present invention relates to naphthol derivativesrepresented by the general formula (IV) ##STR3## or (IV'): ##STR4##wherein one of Y and Y' is --(CONH)_(n) --X and the other is--(CONH)_(n) --X or COR in the general formula (I) X, n and R are asdefined above!.

More particularly, the present invention relates to naphthol derivativesrepresented by the general formula (V): ##STR5## wherein Y and Y' arerespectively represented by COR and COR' in the general formula (I) Rand R' are as defined above, provided that R₂ and Z are notsimultaneously hydrogen atom when R and R' simultaneously are hydroxylgroup!.

The naphthol derivative (I) of the present invention is a novel naphtholderivative compound.

The naphthol derivatives (IV) and (IV') of the present invention arenovel compounds, and are compounds wherein an optionally substitutedphenyl, naphthyl, anthraquinonyl, benzimidazolonyl or carbazolyl groupis added at the 3-position and/or 6-position of 2-hydroxynaphthalenethrough an aminocarbonyl or --CONHCONH group. These residues, which areadded through the aminocarbonyl or --CONHCONH group, may be the same ordifferent at the 3-position and 6-position. The aminocarbonyl or--CONHCONH group as a coupling group may also be the same or differentat the 3-position and 6-position. Regarding the naphthol derivative ofthe present invention, one of the 3-position and 6-position may be ahydroxycarbonyl group, an optionally branched alkoxycarbonyl grouphaving 1 to 6 carbon atoms, a benzyloxycarbonyl group, aphenyloxycarbonyl group or a phenacyloxycarbonyl group. The hydrogenatom of the hydroxyl group at the 2-position may be substituted with analkaline metal atom, an optionally branched alkyl group having 1 to 6carbon atoms, an acyl group having 1 to 6 carbon atoms or aphenyl-substituted alkylene group. One or more sorts selected from thegroup consisting of a halogen atom, a nitro group, a nitroso group andan amino group may be introduced into the naphthalene ring.

When X is a substituted form of the phenyl, naphthyl, anthraquinonyl,benzimidazolonyl or carbazolyl group, examples of the substituentinclude alkyl group, alkoxy group, alkyl halide group, phenoxy group,alkoxycarbonyl group, nitro group, halogen atom, hydroxyl group, aminogroup, benzoylamino group, dialkylaminosulfonyl group or cyano group. Asthe alkyl group, an optionally branched saturated or unsaturated alkylgroup having 1 to 6 carbon atoms can be used. Preferred examples thereofinclude methyl, ethyl, propyl, isopropyl, butyl and t-butyl. As thealkoxy group, an optionally branched saturated or unsaturated alkoxygroup having 1 to 6 carbon atoms can be used. Preferred examples thereofinclude methoxy or ethoxy group. Examples of the halogen atom includefluorine, chlorine, bromine and iodine. The number of the substituent isfrom 1 to 5, and the substituent may be the same or different.

The naphthol derivative (V) of the present invention is also a novelcompound, and a compound wherein a hydroxyl group, a halogen atom, anoptionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxygroup, a phenyloxy group or a phenacyloxy group is added at the3-position and 6-position of 2-hydroxynaphthalene through a carbonylgroup. The substituents at the 3-position and 6-position may be the sameor different. The hydrogen atom of the hydroxyl group at the 2-positionmay be substituted with an alkaline metal atom, an optionally branchedalkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6carbon atoms or a phenyl-substituted alkylene group. One or more sortsselected from the group consisting of a halogen atom, a nitro group, anitroso group and an amino group may be introduced into the naphthalenering.

The above naphthol derivative (IV) or (IV') of the present invention canbe produced by condensing a naphthol derivative represented by thegeneral formula (II): ##STR6## wherein R₄ is a hydroxyl group or ahalogen atom; R₄ ' is a hydroxyl group, a halogen atom or an optionallybranched alkoxy group having 1 to 6 carbon atoms; R₅ is a hydrogen atomor a protective group of a hydroxyl group; and Z is as defined above!,with an aniline compound represented by the general formula (III):

    H.sub.2 N--R.sub.3 --X                                     (III)

wherein R₃ is a single bond or --CONH--; provided that X is as definedabove!.

R₅ in the compound of the formula (II) is a hydrogen atom, an alkalinemetal atom or a protective group of a hydroxyl group. The protectivegroup of the hydroxyl group means a group capable of temporarily bondingto a hydroxyl group during the reaction of introducing a substituentinto the substitution position which is different from that of theprotective group so as to protect the hydroxyl group and then recoveringthe hydroxyl group easily due to alkaline or acid hydrolysis after thecompletion of the desirable reaction. Examples thereof includeoptionally branched alkyl group having 1 to 6 carbon atoms, benzylgroup, acetyl group, acetonyl group, tetrahydropyranyl group,trimethylsilyl group and the like.

A phenylurea derivative, wherein R₃ in the compound of the formula (III)is --CONH--, can be obtained by forming an ureido group using a cyanateprocess of reacting the corresponding aniline compound with cyanic acid.

More specifically, as shown in the reaction scheme (VI): ##STR7##wherein A is hydrogen or a suitable substituent!, the phenylureaderivative can be obtained, for example, by dissolving an anilinecompound in an aqueous acetic acid solution, adding dropwise an aqueouspotassium cyanate solution at 15° C. over 30 minutes, heating to 30° C.after the completion of the dropwise addition, reacting the mixture for30 minutes, filtering the deposited crystal, followed by washing withwater.

The reaction between the compound (II) and compound (III) can beconducted, for example, by charging2-hydroxy-3,6-dihydroxycarbonylnaphthalene and an aniline compound in axylene solvent and adding dropwise PCl₃ at 90° to 100° C. Then, thetemperature is raised to 140° C. and the reaction is conducted for 3hours and, after the completion of the reaction, water is added. Afterneutralizing, the crystal formed by the reaction is filtered and thecrystal on a filter paper is washed with an organic solvent (e.g.xylene, etc.) to obtain a compound (IV) or (IV').

In order to introduce a substituent other than the hydrogen atom intoR₂, for example, a corresponding 3,6-derivative of2-hydroxy-3,6-dihydroxycarbonylnaphthalene may be reacted with a halideof a residue to be introduced (e.g. benzyl chloride, ethyl iodide, etc.)in the state that the 3-position and 6-position are protected, in thepresence of a suitable basic substance (e.g. potassium carbonate, etc.).

In order to introduce halogen at the 1-position, for example, a solutionprepared by dissolving a halogen molecule (e.g. bromine, etc.) inchloroform may be added to a solution of a corresponding compound whose1-position is not substituted. In order to introduce a nitroso group, asolution of the corresponding compound whose 1-position is notsubstituted may be reacted with an aqueous solution of sodium nitrate.

The naphthol derivative (V) of the present invention can be prepared,for example, by reacting known 2-hydroxy-3,6-dihydroxycarbonylnaphthalene represented by the general formula (VII): ##STR8## or1-position and/or 2-position substitution products thereof as a startingsubstance with an organic halide in the presence of a base, or reactinga compound represented by the general formula (VIII): ##STR9## as anacid chloride, which is obtained by chlorinating the compound of thegeneral formula (VII), with alcohols such as lower alcohol having 1 to 6carbon atoms.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 1.

FIG. 2 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 2.

FIG. 3 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 3.

FIG. 4 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 4.

FIG. 5 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 5.

FIG. 6 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 6.

FIG. 7 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 7.

FIG. 8 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 8.

FIG. 9 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 9.

FIG. 10 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 10.

FIG. 11 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 11.

FIG. 12 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 12.

FIG. 13 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 13.

FIG. 14 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 14.

FIG. 15 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 15.

FIG. 16 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 16.

FIG. 17 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 17.

FIG. 18 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 18.

FIG. 19 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 19.

FIG. 20 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 20.

FIG. 21 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 21.

FIG. 22 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 22.

FIG. 23 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 23.

FIG. 24 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 24.

FIG. 25 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 25.

FIG. 26 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 26.

FIG. 27 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 27.

FIG. 28 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 28.

FIG. 29 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 29.

FIG. 30 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 30.

FIG. 31 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 31.

FIG. 32 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 32.

FIG. 33 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 33.

FIG. 34 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 34.

FIG. 35 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 35.

FIG. 36 is a graph illustrating an infrared absorption spectrum of thecompound obtained in Example 36.

EMBODIMENTS OF THE INVENTION

The following Examples further illustrate the present invention indetail.

EXAMPLE 1

Synthesis of 2-hydroxy-3,6-di-2-chlorophenylaminocarbonylnaphthalene##STR10##

2-Hydroxy-3,6-dihydroxycarbonylnaphthalene (11.6 g) and o-chloroaniline(14.0 g) were dispersed in xylene (232.2 g), followed by heating to 90°C. Phosphorous trichloride (6.0 g) was added dropwise at 90° to 110° C.,and then the mixture was reacted at 140° C. for 3 hours. After thecompletion of the reaction, water (116.1 g) was added and the reactionsolution was neutralized with sodium carbonate at 80° to 90° C. Thesolution was filtered at room temperature and washed in turn with xylene(116.1 g) and water (116.1 g). The resultant crystal was subjected toreflux washing using acetone (80 g) and then filtered. This operationwas repeated three times, followed by drying to obtain 14.0 g of2-hydroxy-3,6-di-2-chlorophenylaminocarbonylnaphthalene as a grayishwhite powdered crystal (melting point: 267°-269° C.)

An infrared spectrum (KBr method) of this compound is shown in FIG. 1.

EXAMPLE 2

Synthesis of 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene ##STR11##

2-Hydroxy-3,6-dihydroxycarbonylnaphthalene (4.64 g) and aniline (4.10 g)were dispersed in xylene (92.8 9), followed by heating to 90° C.Phosphorous trichloride (2.4 g) was added dropwise at 90° to 100° C.,and then the mixture was reacted at 140° C. for 3 hours. After thecompletion of the reaction, water (92.8 g) was added and the reactionsolution was neutralized with sodium carbonate at 90° C. The solutionwas filtered at room temperature and washed in turn with xylene (46.4 g)and water (46.4 g). The resultant crystal was subjected to refluxwashing using acetone (80 g) and then filtered. This operation wasrepeated three times, followed by drying to obtain 3.5 g of2-hydroxy-3,6-diphenylaminocarbonylnaphthalene as a white powderedcrystal (melting point: 314°-317° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 2.

EXAMPLE 3

Synthesis of2-hydroxy-3,6-bis(2,4-dimethylphenylaminocarbonyl)naphthalene ##STR12##

2-Hydroxy-3,6-dihydroxycarbonylnaphthalene (11.6 g) and m-xylidine (13.3g) were dispersed in xylene (232.2 g), followed by heating to 90° C.Phosphorous trichloride (6.0 g) was added dropwise at 90° to 100° C.,and then the mixture was reacted at 140° C. for 3 hours. After thecompletion of the reaction, water (116.1 g) was added and the reactionsolution was neutralized with sodium carbonate at 80° to 90° C. Thesolution was filtered at room temperature and washed in turn with xylene(116.1 g) and water (116.1 g). The resultant crystal was subjected toreflux washing using acetone (80 g) and then filtered. This operationwas repeated three times, followed by drying to obtain 12.9 g of2-hydroxy-3,6-bis(2,4-dimethylphenylaminocarbonyl)naphthalene as a whitepowdered crystal (melting point: 284.5°-286° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 3.

EXAMPLE 4

Synthesis of 2-hydroxY-3,6-di-2-methylphenylaminocarbonylnaphthalene##STR13##

2-Hydroxy-3,6-dihydroxycarbonylnaphthalene (11.6 g) and o-toluidine(12.0 g) were dispersed in xylene (232.2 g), followed by heating to 90°C. Phosphorous trichloride (6.0 g) was added dropwise at 90° to 110° C.,and then the mixture was reacted at 140° C. for 3 hours. After thecompletion of the reaction, water (116.1 g) was added and the reactionsolution was neutralized with sodium carbonate at 80° to 90° C. Thesolution was filtered at room temperature and washed in turn with xylene(116.1 g) and water (116.1 g). The resultant crystal was subjected toreflux washing using acetone (80 g) and then filtered. This operationwas repeated three times, followed by drying to obtain 7.8 g of2-hydroxy-3,6-di-2-methylphenylaminocarbonylnaphthalene as a whitepowdered crystal (melting point: 264.5°-268° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 4.

EXAMPLE 5

Synthesis of 2-hydroxy-3,6-di-2-methoxyphenylaminocarbonylnaphthalene##STR14##

2-Hydroxy-3,6-dicarbonylnaphthalene (11.6 g) and o-anisidine (13.5 g)were dispersed in xylene (232.2 g), followed by heating to 90° C.Phosphorous trichloride (6.0 g) was added dropwise at 90° to 110° C.,and then the mixture was reacted at 140° C. for 3 hours. After thecompletion of the reaction, water (116.1 g) was added and the reactionsolution was neutralized with sodium carbonate at 80° to 90° C. Thesolution was filtered at room temperature and washed in turn with xylene(116.1 g) and water (116.1 g). The resultant crystal was subjected toreflux washing using acetone (80 g) and then filtered. This operationwas repeated three times, followed by drying to obtain 5.8 g of2-hydroxy-3,6-di-2-methoxyphenylaminocarbonylnaphthalene as a whitepowdered crystal (melting point: 206°-210° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 5.

EXAMPLE 6

Synthesis of 2-hydroxy-3,6-dichlorocarbonylnaphthalene ##STR15##

After 2-hydroxy-3,6-dihydroxycarbonylnaphthalene (24.0 g) anddimethylformamide (0.08 g) were added in xylene (410 g), thionylchloride (66.2 g) was added dropwise at 20° C. over 60 minutes. Themixture was heated to 70° C. and then reacted for 21 hours. Then, xyleneand excess thionyl chloride were distilled off under reduced pressure toobtain 28.6 g of an acid chloride.

An infrared spectrum (KBr method) of this compound is shown in FIG. 6.

EXAMPLE 7

Synthesis of 2-hydroxy-3,6-di-2-chlorophenylureidocarbonylnaphthalene##STR16##

(1) Synthesis of o-chlorophenylurea ##STR17##

O-chloroaniline (50 g) was added in water (400 g) and acetic acid (200g), followed by cooling to 15° C. Then, a solution of potassium cyanate(63.6 g) and water (300 g) was added dropwise at not more than 15° C.over 40 minutes. The mixture was heated to 30° C., filtered and thenwashed with cold water to obtain a white crystal. This crystal wasrecrystallized from a solution of ethanol (350 g) and water (100 g) toobtain 47.1 g of o-chlorophenylurea as a white needle crystal.

(2) Synthesis of2-hydroxy-3,6-di-2-chlorophenylureidocarbonylnaphthalene

The acid chloride prepared according to the process of Example 6, i.e.2-hydroxy-3,6-dichlorocarbonylnaphthalene (5.9 g) was gradually added toa suspension of the o-chlorophenylurea (7.5 g) obtained above andtoluene (150 g) at 20° C. After pyridine (3.5 g) was added, the mixturewas heated to 90° C. and reacted for 16 hours. Then, the reactionsolution was cooled to 15° C. and filtered. The resultant product wassubjected to reflux washing for 5 hours using acetone (100 g), filteredand then dried to obtain 8.8 g of2-hydroxy-3,6-di-2-chlorophenylureidocarbonylnaphthalene as a paleyellow powdered crystal (melting point: 213.2°-222.4° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 7.

EXAMPLE 8

Synthesis of 2-hydroxy-3,6-di-4-phenoxyphenylaminocarbonylnaphthalene##STR18##

To a solution of 4-aminodiphenyl ether (11.2 g), N-methyl-2-pyrrolidone(75.5 g) and toluene (30.2 g) was gradually added the acid chloride (5.5g) obtained in Example 6, and then the mixture was heated to 90° C. andreacted for 25 hours. After the reaction solution was cooled to 25° C.and filtered, toluene was distilled off under reduced pressure. Then,the solution was crystallized by using methanol (158.1 g) and filtered.The resultant product was subjected to reflux washing using methanol(200.0 g) for 1 hour, filtered and then dried to obtain 9.2 g of2-hydroxy-3,6-di-4-phenoxyphenylaminocarbonylnaphthalene as a pale beigepowdered crystal (DSC analysis value: 314.8° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 8.

EXAMPLE 9

Synthesis of2-hydroxy-3,6-di-anthraquinone-2-yl-aminocarbonylnaphthalene ##STR19##

2-Aminoanthraquinone (14.5 g), N-methyl-2-pyrrolidone (145.6 g) andtoluene (40.0 g) were dissolved by heating to 60° C. and the acidchloride (5.5 g) obtained in Example 6 was gradually added, and then themixture was amidated according to Example 8. After the reaction solutionwas cooled to 25° C. and filtered, toluene was distilled off underreduced pressure. Then, the solution was crystallized by using methanol(244.3 g). The resultant product was subjected to reflux washing usingacetone (320.2 g) for 1 hour, filtered and then dried to obtain 11.0 gof 2-hydroxy-3,6-di-anthraquinone-2-yl-aminocarbonylnaphthalene as anolive powdered crystal (DSC analysis value: 367.2° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 9.

EXAMPLE 10

Synthesis of2-hydroxy-3,6-bis(2,5-dimethoxy-4-benzoylaminophenyl-aminocarbonyl)naphthalene##STR20##

2,5-Dimethoxy-4-benzoylaminoaniline (16.6 g), N-methyl-2-pyrrolidone(111.2 g) and toluene (30.1 g) were dissolved at room temperature andthe acid chloride (5.5 g) obtained in Example 6 was gradually added, andthen the mixture was amidated according to Example 8. After the reactionsolution was cooled to 25° C. and filtered, toluene was distilled offunder reduced pressure. Then, the solution was crystallized by usingmethanol (377.2 g). The resultant product was subjected to refluxwashing using methanol (250.0 g) for 1 hour, filtered and then dried toobtain 12.4 g of2-hydroxy-3,6-bis(2,5-dimethoxy-4-benzoylaminophenyl-aminocarbonyl)naphthaleneas a dull yellow powdered crystal (DSC analysis value: 327.4° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 10.

EXAMPLE 11

Synthesis of2-hydroxy-3,6-di-2-methoxycarbonylphenyl-aminocarbonylnaphthalene##STR21##

Methyl-2-aminobenzoate (9.3 g), N-methyl-2-pyrrolidone (169.8 g) andtoluene (136.0 g) were dissolved at room temperature and the acidchloride (5.5 g) obtained in Example 6 was gradually added, and then themixture was amidated at 90° C. for 22 hours. After the reaction solutionwas cooled to 25° C. and filtered, toluene was distilled off underreduced pressure. Then, the solution was crystallized by using methanol(226.7 g). The resultant product was subjected to reflux washing usingmethanol (199.4 g) for 1 hour, filtered and then dried to obtain 8.0 gof 2-hydroxy-3,6-di-2-methoxycarbonylphenyl-aminocarbonylnaphthalene asa light yellow powdered crystal (DSC analyswas value: 239.6° C.).

An infrared spectrum (KBr method) of thwas compound is shown in FIG. 11.

EXAMPLE 12

Synthesis of2-hydroxy-3,6-bis(2-methoxy-5-diethylaminosulfonyl-aminocarbonyl)naphthalene##STR22##

3-Amino-4-methoxydiethylaminosulfonylbenzene (15.6 g),N-methyl-2-pyrrolidone (86.1 g) and toluene (34.3 g) were dissolved atroom temperature and the acid chloride (5.4 g) obtained in Example 6 wasgradually added, and then the mixture was amidated at 90° C. for 24hours. After the reaction solution was cooled to 25° C. and filtered,toluene was distilled off under reduced pressure. Then, the solution wascrystallized by using methanol (350.1 g). The resultant product wasfiltered and then dried to obtain 8.9 g of2-hydroxy-3,6-bis(2-methoxy-5-diethylaminosulfonylphenyl-aminocarbonyl)naphthaleneas a cream powdered crystal (DSC analysis value: 245.0° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 12.

EXAMPLE 13

Synthesis of2-hydroxy-3.6-di-benzimidazolon-5-yl-aminocarbonylnaphthalene ##STR23##

To a solution of 5-aminobenzimidazolone (13.5 g), N-methyl-2-pyrrolidone(99.0 g) and toluene (44.8 g) was gradually added the acid chloride (8.1g) obtained in Example 6, and then the mixture was amidated at 90° C.for 29 hours. The reaction solution was cooled to 25° C., filtered andthen washed with methanol. The resultant crystal was dissolved inN-methyl-2-pyrrolidone (441.9 g) at 120° C. and carborafine (2.1 g) wasadded, and then the mixture was carbon-treated at 120° C. for 1 hour.After carbon was removed by filtration, the solution was cooled andcrystallized by using methanol (146.4 g). The resultant product wasfiltered and then dried to obtain 11.8 g of2-hydroxy-3,6-di-benzimidazolon-5-yl-aminocarbonylnaphthalene as ayellowish green powdered crystal (DSC analysis value: 421.4° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 13.

EXAMPLE 14

Synthesis of 2-hydroxy-3,6-di-3-nitrophenylaminocarbonylnaphthalene##STR24##

m-Nitroaniline (8.38 g), N-methyl-2-pyrrolidone (65.5 g) and toluene(30.3 g) were dissolved at room temperature and the acid chloride (5.5g) obtained in Example 6 was gradually added, and then the mixture wasamidated at 90° C. for 24 hours. After the reaction solution was cooledto 25° C. and filtered, toluene was distilled off under reducedpressure. Then, the solution was crystallized by using methanol (197.3g), filtered and dried. The resultant product was subjected to refluxwashing using methanol (263.4 g) for 1 hour, filtered and then dried toobtain 7.8 g of 2-hydroxy-3,6-di-3-nitrophenylaminocarbonylnaphthaleneas a cream powdered crystal (DSC analysis value: 342.9° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 14.

EXAMPLE 15

Synthesis of2-hydroxy-3,6-di-9-ethylcarbazol-3-yl-aminocarbonylnaphthalene ##STR25##

3-Amino-9-ethylcarbazole (12.8 g), N-methyl-2-pyrrolidone (65.6 g) andtoluene (30.4 g) were dissolved at room temperature and the acidchloride (4.1 g) obtained in Example 6 was gradually added, and then themixture was amidated at 90° C. for 23 hours. After the reaction solutionwas cooled to 25° C. and filtered, toluene was distilled off underreduced pressure. Then, the solution was crystallized by using methanol(422.9 g) and filtered, and the resultant crystal was subjected toreflux washing using methanol (200.5 g) for 1 hour, filtered and dried.The resultant product was dissolved in N-methyl-2-pyrrolidone (90.4 g)at 120° C. and carborafine (1.0 g) was added, and then the mixture wascarbon-treated at 120° C. for 1 hour. After carbon was removed byfiltration, the solution was cooled and crystallized by using methanol(301.8 g). The resultant product was filtered and then dried to obtain3.7 g of 2-hydroxy-3,6-di-9-ethylcarbazol-3-yl-aminocarbonylnaphthaleneas a grayish yellowgreen powdered crystal (TG decomposition point:417.2° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 15.

EXAMPLE 16

Synthesis of2-hydroxy-3,6-bis(3-trifluoromethylphenyl-aminocarbonyl)naphthalene##STR26##

3-Aminotrifluoromethylbenzene (9.7 g), N-methyl-2-pyrrolidone (65.2 g)and toluene (30.0 g) were dissolved at room temperature and the acidchloride (5.5 g) obtained in Example 6 was gradually added, and then themixture was amidated at 90° C. for 24 hours. The reaction solution wasdried under reduced pressure, dissolved in methyl ethyl ketone (317.4 g)and then washed three times with aqueous 8% hydrochloric acid (167.1 g).The solution was crystallized by using water (418.2 g), filtered andthen dried. The product was dissolved in N-methyl-2-pyrrolidone (56.8 g)at 120° C. and carborafine (0.8 g) was added, and then the mixture wascarbon-treated at 120° C. for 1 hour. After carbon was removed byfiltration, the solution was cooled and crystallized by using water(164.6 g) and then filtered. The resultant product was dissolved inethyl acetate (202.1 g) and xylene (123.6 g) was added, and then themixture was concentrated, cooled and crystallized. The resultant productwas filtered and then dried to obtain 4.9 g of2-hydroxy-3,6-bis(3-trifluoromethylphenyl-aminocarbonyl)naphthalene as apale beige powdered crystal (TG decomposition point: 256.4° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 16.

EXAMPLE 17

Synthesis of 2-hydroxy-3,6-di-1-naphthylaminocarbonylnaphthalene##STR27##

1-Napahthylamine (8.6 g), N-methyl-2-pyrrolidone (60.0 g) and toluene(30.0 g) were dissolved at room temperature and the acid chloride (5.5g) obtained in Example 6 was gradually added, and then the mixture wasamidated at 90° C. for 20 hours. After the reaction solution was cooledto 25° C. and filtered, toluene was distilled off under reducedpressure. Then, the solution was crystallized by using methanol (209.6g) and subjected to reflux washing. After the solution was filtered anddried, the resultant product was dissolved in N-methyl-2-pyrrolidone(57.9 g) at 120° C. and carborafine (3.0 g) was added, and then themixture was carbon-treated at 120° C. for 1 hour. After carbon wasremoved by filtration, the solution was concentrated, crystallized byusing methanol (51.7 g), filtered and then dried to obtain 5.5 g of2-hydroxy-3,6-di-1-naphthylaminocarbonylnaphthalene as a grayish olivepowdered crystal (DSC analysis value: 292.1° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 17.

EXAMPLE 18

Synthesis of2-hydroxy-3,6-bis(pentafluorophenyl-aminocarbonyl)naphthalene ##STR28##

Pentafluoroaniline (9.1 g), N-methyl-2-pyrrolidone (60.1 g) and toluene(30.0 g) were dissolved at room temperature and the acid chloride (4.5g) obtained in Example 6 was gradually added, and then the mixture wasamidated at 50° C. for 21 hours according to Example 8. After thereaction solution was dried under reduced pressure and dissolved inmethanol (980.1 g) at the reflux temperature, carborafine (5.0 g) wasadded and the mixture was carbon-treated for 1 hour. The resultantproduct was concentrated, cooled, crystallized, filtered and then driedto obtain 2.3 g of2-hydroxy-3,6-bis(pentafluorophenyl-aminocarbonyl)naphthalene as a whitepowdered crystal (TG decomposition point: 305.7° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 18.

EXAMPLE 19

Synthesis of2-benzyloxy-3,6-bis(2,5-dimethoxy-4-benzoylamino-phenylaminocarbonyl)naphthalene##STR29##

2-Hydroxy-3,6-bis(2,5-dimethoxy-4-benzoylamino-phenylaminocarbonyl)naphthalene(2.5 g) obtained in Example 10 was mixed with N,N-dimethylformamide (30g) and the mixture was dissolved by heating to 100° C. under a nitrogenatmosphere. To the solution, potassium carbonate (0.5 g) was graduallyadded and benzyl chloride (0.46 g) was added dropwise and the mixedsolution was reacted for 5 hours. After the completion of the reaction,the reaction solution was cooled to room temperature, filtered and thenwashed with water and methanol to obtain 2.65 g of2-benzyloxy-3,6-bis(2,5-dimethoxy-4-benzoylamino-phenylaminocarbonyl)naphthaleneas a greenish yellow crystal (DSC analysis value: 282.8° C.)

An infrared spectrum (KBr method) of this compound is shown in FIG. 19.

EXAMPLE 20

Synthesis of 2-ethoxy-3,6-di-4-phenoxyphenylaminocarbonylnaphthalene##STR30##

2-Hydroxy-3,6-di-4-phenoxyphenylaminocarbonylnaphthalene (2.83 g)obtained in Example 8 was mixed with N,N-dimethylformamide (30 g) andthe mixture was dissolved by heating to 70° C. under a nitrogenatmosphere. To the solution, potassium carbonate (0.38 g) was graduallyadded and ethyl iodide (0.87 g) was added dropwise and the mixedsolution was reacted for 10 hours. After the completion of the reaction,the reaction solution was cooled to room temperature, poured into water(300 g) dropwise, filtered and then washed with water and methanol toobtain 2.81 g of 2-ethoxy-3,6-di-4-phenoxyphenylaminocarbonylnaphthaleneas a grayish brown crystal (DSC analysis value: 177.6° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 20.

EXAMPLE 21

Synthesis of1-bromo-2-hydroxy-3,6-di-3-nitrophenylaminocarbonynaphthalene ##STR31##

2-Hydroxy-3,6-di-3-nitrophenylaminocarbonylnaphthalene (2.4 g) obtainedin Example 14, chloroform (40 g), dimethyl sulfoxide (20 g) andN-methyl-2-pyrrolidone (20 g) were mixed and dissolved. Then, a solutionof bromine (0.8 g) and chloroform (10 g) was added dropwise at 5° C.over 1 hour. After the dropwise addition, the mixture was continuouslycooled, filtered at 3° C., washed with water and cold methanol and thendried under vacuum to obtain 2.7 g of1-bromo-2-hydroxy-3,6-di-3-nitrophenylaminocarbonylnaphthalene as awhitish yellow powdered crystal (DSC analysis value: 325.3° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 21.

EXAMPLE 22

Synthesis of 1-bromo-2-hydroxy-3,6-dihydroxycarbonylnaphthalene##STR32##

2-Hydroxy-3,6-di-hydroxycarbonylnaphthalene (11.8 g) was dissolved inchloroform (300 g) and dimethyl sulfoxide (100 g), followed byice-cooling. Then, a solution of bromine (8.0 g) and chloroform (50 g)was added dropwise at not more than 5° C. over 2 hours. Aftercontinuously stirring for 1 hour, this solution was poured into water(1500 g) dropwise. The deposit was filtered and then washed with waterand dispersed in a small amount of methanol. The dispersion wasconcentrated under reduced pressure at room temperature and then driedunder vacuum to obtain 15.1 g of1-bromo-2-hydroxy-3,6-di-hydroxycarbonylnaphthalene as a whitish browncrystal (DSC analysis value: 145.2° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 22.

EXAMPLE 23

Synthesis of 1-bromo-2-hydroxy-3,6-di-chlorocarbonylnaphthalene##STR33##

1-Bromo-2-hydroxy-3, 6-di-hydroxycarbonylnaphthalene (3.2 g) obtained inExample 22 was dispersed in xylene (100 g) and N,N-dimethylformamide(0.1 g) was further added. Then, a solution of thionyl chloride (6.8 g)and xylene (30 g) was added dropwise over about 30 minutes. Then, themixture was heated to 70° C. and reacted for 2.5 hours. The insolubleunreacted raw material was removed by filtration, and then xylene andexcess thionyl chloride were distilled off under reduced pressure toobtain 3.5 g of an acid chloride (DSC analysis value: 162.0° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 23.

EXAMPLE 24

Synthesis of 2-benzyloxy-3.6-di-benzyloxycarbonylnaphthalene ##STR34##

2-Hydroxy-3,6-di-hydroxycarbonylnaphthalene (2.4 g) was dissolved indimethylformamide (50 g), followed by heating to 100° C. Potassiumcarbonate (4.6 g) was slowly added and benzyl chloride (4.2 g) was addeddropwise. After heating for about 20 hours, the reaction solution waspoured into a mixed solution of water (300 g) and methanol (100 g). Thedeposit was filtered and then washed with water to obtain 3.5 g of2-benzyloxy-3,6-di-benzyloxycarbonylnaphthalene as whitish yellow powder(DSC analysis value: 100.5° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 24.

EXAMPLE 25

Synthesis of1-nitroso-2-hydroxy-3,6-bis(2,4-dimethylphenylaminocarbonyl)naphthalene##STR35##

2-Hydroxy-3,6-bis(2,4-dimethylphenylaminocarbonyl)-naphthalene (1.5 g)obtained in Example 3 was dissolved in acetic acid (7.0 g), ethanol (7.0g) and N-methyl-2-pyrrolidone (18.0 g), followed by cooling to 0° C. Asolution prepared by dissolving sodium nitrite (0.97 g) in water (4.2 g)was added dropwise at 0° to 1° C. and then the mixture was reacted atthe same temperature for 2 hours. After stirring at room temperatureovernight, the deposited crystal was filtered, washed with a smallamount of ethanol and dried under vacuum at 50° C. to obtain 1.4 g of acolored crystal. This crystal (1.4 g) was dissolved inN-methyl-2-pyrrolidone (58.3 g) with heating, treated with active carbon(0.09 g) and then subjected to thermal filtration. The filtrate wasdiluted with methanol to deposit a crystal, which was filtered, washedwith methanol and then dried to obtain 0.58 g of pale brown1-nitroso-2-hydroxy-3,6-bis(2,4-dimethylaminocarbonyl)-naphthalene (DSCanalysis value: 267.3° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 25.

EXAMPLE 26

Synthesis of 2-hydroxy-3,6-dimethoxy-carbonylnaphthalene ##STR36##

2-Hydroxy-3,6-dichlorocarbonylnaphthalene (12.0 g) obtained in Example 6was mixed with methanol (600 g) and, after refluxing for 2 hours, activecarbon (1.0 g) was added and the mixture was subjected to thermalfiltration. The filtrate was cooled to deposit a crystal, which wasfiltered and then dried to obtain 8.3 g of a crude crystal. The crudecrystal was purified with methanol (300 g) to obtain 4.0 g of2-hydroxy-3,6-dimethoxycarbonylnaphthalene as a pale yellow crystal (DSCanalysis value: 163.1° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 26.

EXAMPLE 27

Synthesis of 2-hydroxy-3-hydroxycarbonyl-6-methoxycarbonylnaphthalene##STR37##

2-Hydroxy-3,6-di-hydroxycarbonylnaphthalene (11.6 g) was dispersed inanhydrous acetonitrile (116.0 g) and N-methyl-2-pyrrolidone (39.0 g).Then, methyl iodide (7.85 g) was added and 1.8-diazabicyclo5.4.0!undec-7-ene (hereinafter referred to as "DBU") (8.37 g) was addeddropwise over 5 minutes, followed by heating at 50° C. overnight.Further methyl iodide (2.32 g) and DBU (2.42 g) was added and mixturewas stirred overnight. The deposited crystal was filtered and then driedunder reduced pressure to obtain 7.29 g of a crude crystal of2-hydroxy-3-hydroxycarbonyl-6-methoxycarbonylnaphthalene. Aliquot ofthis crystal (1.52 g) was dissolved in ethyl acetate (30.2 g) and anaqueous 5% sodium hydrogencarbonate. The solution was separated into theorganic layer and the aqueous layer, and then the organic layer wasextracted with an aqueous 5% sodium hydrogencarbonate solution (10.3 g)and aqueous extract was combined with the above aqueous layer. To thisaqueous layer was added dropwise 10% hydrochloric acid until the pHbecomes 7 while ice-cooling. The deposited crystal was filtered and thendried under reduced pressure to obtain 1.02 g of2-hydroxy-3-hydroxycarbonyl-6-methoxycarbonylnaphthalene (DSC analysisvalue: 295.1° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 27.

EXAMPLE 28

Synthesis of2-hydroxy-3-phenylaminocarbonyl-6-methoxycarbonylnaphthalene ##STR38##

2-Hydroxy-3-hydroxycarbonyl-6-methoxycarbony-naphthalene (0.50 g)obtained in Example 27 was suspended in N-methyl-2-pyrrolidone (5.00 g)and dicyclohexylcarbodiimide (hereinafter referred to as "DCC") (0.42 g)and aniline (0.57 g) were added, followed by stirring at roomtemperature overnight. After heating to 50° C., DCC (0.18 g) was furtheradded and the mixture was stirred overnight. The reaction solution wasconcentrated under reduced pressure and the residue was purified twiceby subjecting to silica gel chromatography to obtain 0.65 g of2-hydroxy-3-phenylaminocarbonyl-6-methoxycarbonylnaphthalene (DSCanalysis value: 238.1° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 28.

EXAMPLE 29

Synthesis of sodium 3-phenylaminocarbonyl-6-methoxycarbonyl-2-naphthoate##STR39##

2-Hydroxy-3-phenylaminocarbonyl-6-methoxycarbonyl-naphthalene (0.45 g)obtained in Example 28 was suspended in methanol (10.0 g) and 1N-sodiumhydroxide (2.8 g) was added under ice-cooling. A yellow crystal ofsodium 3-phenylaminocarbonyl-6-methoxycarbonyl-2-naphthoate, which wasonce dissolved and deposited, was filtered and then dried under reducedpressure to obtain 0.32 g of it.

An infrared spectrum (KBr method) of this compound is shown in FIG. 29.

EXAMPLE 30

Synthesis of2-hydroxy-3-phenylaminocarbonyl-6-hydroxycarbonylnaphthalene ##STR40##

Sodium 3-phenylaminocarbonyl-6-methoxycarbonyl-2-naphthoate (0.081 g)obtained in Example 29 was suspended in methanol (8.10 g) and deionizedwater (8.13 g) and 1N-sodium hydroxide (4.0 g) was added dropwise underice-cooling, followed by stirring overnight. The reaction solution wasfreeze-dried and the resultant solid was dissolved in water. Thesolution was acidified with diluted hydrochloric acid and the depositedcrystal was filtered. The crystal was dried under reduced pressure toobtain 0.057 g of2-hydroxy-3-phenylaminocarbonyl-6-hydroxycarbonylnaphthalene.

An infrared spectrum (KBr method) of this compound is shown in FIG. 30.

EXAMPLE 31

Synthesis of2-hydroxy-3-phenacyloxycarbonyl-6-methoxycarbonylnaphthalene ##STR41##

To anhydrous N,N-dimethylformamide (hereinafter referred to as "DMF")(10.0 g) were added potassium fluoride (0.209 g) and phenacyl bromide(0.647 g), followed by stirring on an oil bath at 25° C. for about 1minute. 2-Hydroxy-3-hydroxycarbonyl-6-methoxycarbonylnaphthalene (0.80g) was dissolved in anhydrous DMF (5.20 g) and the resulting solutionwas added to the reaction solution. After the completion of thereaction, ethyl acetate, diethyl ether and aqueous 5% sodiumhydrogencarbonate were added. Then, an insoluble matter was removed byfiltration and the residue was partitioned. The organic layer was washedwith a saturated sodium chloride aqueous solution and then dried overanhydrous magnesium sulfate. After the desiccant was removed byfiltration, the filtrate was concentrated under reduced pressure. Theresultant residue was purified by subjecting to silica gelchromatography to obtain 0.57 g of2-hydroxy-3-phenacyloxycarbonyl-6-methoxycarbonylnaphthalene (DSCanalysis value: 177.7° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 31.

EXAMPLE 32

Synthesis of 2-benzyloxy-3,6-di-methoxycarbonylnaphthalene ##STR42##

2-Hydroxy-3,6-di-methoxycarbonylnaphthalene (2.7 g) obtained in Example26 was dissolved in N,N-dimethylformamide (50 g), followed by heating to100° C. Potassium carbonate (1.5 g) was slowly added and benzyl chloride(1.4 g) was added dropwise. After heating for about 20 hours, thereaction solution was poured into a mixed solution of water (300 g) andmethanol (100 g). The deposit was filtered and then washed with water toobtain 2.5 g of 2-benzyloxy-3,6-di-methoxycarbonylnaphthalene as whitishyellow powder (DSC analysis value: 113.8° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 32.

EXAMPLE 33

Synthesis of 2-benzyloxy-3,6-di-hydroxycarbonylnaphthalene ##STR43##

2-Benzyloxy-3,6-di-methoxycarbonylnaphthalene (0.52 g) obtained inExample 32 was dissolved in N-methyl-2-pyrrodidone (10 g) and methanol(10 g) and water (20 g) were added. Furthermore, an aqueous 1N-sodiumhydroxide (4.5 g) was added, followed by stirring at about 60° C. for 2hours. After the insoluble formed during the reaction was removed byfiltration, the solution was adjusted to about pH 4 using aqueous 10%hydrochloric acid. The deposit was filtered and then washed with waterto obtain 0.41 g of 2-benzyloxy-3,6-di-hydroxycarbonylnaphthalene aspale brown powder (DSC analysis value: 241.3° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 33.

EXAMPLE 34

Synthesis of 2-acetoxy-3,6-di-methoxycarbonylnaphthalene ##STR44##

2-Hydroxy-3,6-di-methoxycarbonylnaphthalene (2.6 g) obtained in Example26 was suspended in acetic anhydride (10.0 g), acetic acid (12.0 g) andN,N-dimethylformamide (20.0 g) and 4-dimethylaminopyridine (0.1 g) wasadded, followed by heating to 50° C. After heating for about 6 hours,the reaction solution was poured into a mixed solution of water (300 g)and methanol (100 g). The deposit was filtered and then washed withwater to obtain 2.55 g of 2-acetoxy-3,6-di-methoxycarbonylnaphthalene aspale yellow powder (DSC analysis value: 130.6° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 34.

EXAMPLE 35

Synthesis of 2-acetoxy-3,6-di-hydroxylcarbonylnaphthalene ##STR45##

2-Hydroxy-3,6-di-hydroxycarbonylnaphthalene (12.1 g) was suspended inacetic anhydride (39.0 g), acetic acid (60.1 g) andN,N-dimethylformamide (40.0 g) and 4-dimethylaminopyridine (0.2 g) wasadded, followed by heating to 50° C. After heating for about 20 hours,the reaction solution was poured into a mixed solution of water (400 g)and methanol (100 g). The deposit was filtered and then washed withwater to obtain 11.6 g of 2-acetoxy-3,6-di-hydroxycarbonylnaphthalene asgrayish white powder (DSC analysis value: 239.2° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 35.

EXAMPLE 36

Synthesis of 2-hydroxy-3,6-di-isopropyloxycarbonylnaphthalene ##STR46##

2-Hydroxy-3,6-di-dichlorocarbonylnaphthalene (1.17 g) obtained inExample 6 was mixed with isopropyl alcohol (30 g), and then the mixturewas heated to 80° C. and maintained at the same temperature for about 30minutes. After the insoluble matter was removed by filtration, thefiltrate was concentrated under reduced pressure and the residue wasrecrystallized by using methanol to obtain 1.36 g of2-hydroxy-3,6-di-isopropyloxycarbonylnaphthalene as pale yellow powder(DSC analysis value: 83.7° C.).

An infrared spectrum (KBr method) of this compound is shown in FIG. 36.

What is claimed is:
 1. A process for producing a naphthol derivativerepresentated by formula (I): ##STR47## R₂ is a hydrogen atom, analkaline metal, an optionally branched alkyl group having 1 to 6 carbonatoms, an acyl group having 1 to 6 carbon atoms or a phenalkylenegroup;wherein 1 of Y and Y' is --(CONH)_(n) --X and the other is--(CONH)_(n) --X or COR, R indicates a hydroxyl group, an optionallybranched alkoxy group having 1 to 6 carbon atoms, a halogen atom, abenzyloxy group, a phenyloxy group or a phenacyloxy group; whichcomprises condensing a naphthol derivative represented by the generalformula (II): ##STR48## wherein one of R₄ and R₄ ' is a hydroxyl groupor a halogen atom and the other is a hydroxyl group, a halogen atom, anoptionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxygroup, a phenyloxy group or a phenacyloxy group; R₅ is a hydrogen atomor a protective group of a hydroxyl group; and Z is at least one groupselected from the group consisting of a hydrogen atom, a halogen atom, anitro group, a nitroso group, and an amino group and Z may besubstituted on any ring of the naphthalene ring; with an anilinecompound represented by a general formula (III):

    H.sub.2 N--R.sub.3 --X                                     (III)

wherein R₃ is a single bond or --CONH-- and each X is independentlyselected from a phenyl group, a naphthyl group, an anthraquinonyl group,a benzimidazolonyl group or a carbazolyl group, and each X group may beoptionally substituted.